Novel onium surfactants

ABSTRACT

Novel onium surfactants are described which correspond to the formula X[(CH 2  CH 2  O-- m  CH 2  --R--CHR&#39;--Q.sup.⊕ A.sup.⊖ ] n , wherein X is an n-valent hydrophobic radical derived by the removal of n-atoms of active hydrogen from an organic compound; m is one or more; R is a divalent aromatic hydrocarbon radical of from 6 to about 14 carbon atoms, the chain-length of which may be interrupted by oxygen or sulfur atoms; R&#39; is hydrogen or methyl and is methyl only when R is m- or p-phenylene; Q.sup.⊕  is a quaternized atom of nitrogen or phosphorus or a tertiary atom of sulfur; A.sup.⊖  is a compatible anion; and n is from 1 to 5. The following compound is an example C 9  H 19  --C 6  H 4  --O--CH 2  CH 2  O-- 15  CH 2  --C 6  H 4  --CH 2  --S.sup.⊕ --CH 3 ) 2  Cl.sup.⊖. The novel surfactants are prepared in two steps. In step 1, various nonionic surfactants are reacted with certain chloromethylated aromatics in the presence of a strong base to give novel intermediates which are subsequently reacted in step 2 with tertiary amines, pyridines, tertiary phosphines, sulfides, thiourea etc. to give the onium surfactants.

CROSS REFERENCE TO RELATED APPLICATION

This is a division, of aplication Ser. No. 895,558 filed 4/12/78 whichis a division of application Ser. No. 416,308, filed 11/15/73 (now U.S.Pat. No. 4,093,663).

BACKGROUND OF THE INVENTION

This invention pertains to novel onium surfactants and the precursorsthereof.

Surface active agents (surfactants) have been defined as any compoundthat reduces surface tension when dissolved in water or water solutions,or which reduces interfacial tension between two liquids, or between aliquid and a solid. See "The Condensed Chemical Dictionary," EighthEdition by G. G. Hawley, Van Nostrand Reinhold Co., N.Y. (1971).Surfactants are useful as detergents, wetting agents and/or emulsifiersand are normally described as being either ionic (cationic or anionic)or nonionic surfactants. The nonionic surfactants are of particularinterest in the instant invention.

The nonionic surfactants form a known class of compounds having manymembers. Those having an end block(s) of polyoxyethylene unitsterminated with a hydroxyl group (i.e. --CH₂ CH₂ O--_(m) H) areparticularly useful commercially. Such compounds are normally preparedby condensing ethylene oxide (EO) onto a hydrophobic (lyophilic)compound bearing at least one active hydrogen. By "active hydrogen" ismeant hydrogen active in the Zerewitinoff reaction. E.g. hydrogen on acarboxyl group, a phenolic hydroxyl group, a mercaptan group, etc. areactive hydrogens). The nonionic surfactants are also characterized bytheir hydrophiliclyophilic balance (HLB).

The concept of HLB is now widely accepted, particularly for the nonionicsurfactants, and is fully described in the literature. See, for example,the text "Emulsions--Theory and Practice," 2nd Ed., A.C.S. Monograph No.162, by Paul Becher, Reinhold Publishing Corp., N.Y. (1965), pp.232-255.

A wide variety of nonionic surfactants are described in "McCutcheon'sDetergents and Emulsifiers--1972 Annual," published by McCutcheon'sDivision, Allured Publishing Corp., N.J. (1972) and in "NonionicSurfactants," Vol. 1 of the "Surfactant Science Series," edited by M. J.Schiek, published by Marcel Dekker, Inc., N.Y. (1967).

The known class of nonionic surfactants whose members have from 1 to 5end blocks of polyoxyethylene units terminated with hydroxyl and havingan HLB of from 1 to about 30 (preferably from about 5 to about 18) areused herein as reactants leading to the novel onium surfactants. Thisclass of nonionic surfactants is represented by the formula ##STR1##wherein X is an n-valent hydrophobic radical derived by the removal ofn-atoms of active hydrogen from an organic compound, m is an integer ofat least 1 and is normally from 1 to about 200 and is most frequentlyfrom 4 to about 50; and n is an integer of from 1 to 5. The reactantshaving from 1 to 3 end blocks of polyoxyethylene units (i.e. n is 1, 2or 3) are currently preferred and those having only one (n is 1) endblock of polyoxyethylene units are most preferred. The latter compoundsare referred to as monofunctional nonionic surfactants.

SUMMARY OF THE INVENTION

A novel class of onium surfactants, and precursors thereof, has now beendiscovered.

The novel onium surfactants are represented by the formula ##STR2##wherein X, m and n have the aforesaid meaning; R is a divalent aromatichydrocarbon radical of from 6 to about 14 carbon atoms (preferably 6 to12 carbon atoms), the chain-length of which can be interrupted by oxygenor sulfur atoms; R' is hydrogen or methyl and is methyl only when R ism- or p-phenylene, Q.sup.⊕ is a quaternized atom of nitrogen orphosphorus or a tertiary atom of sulfur; and A.sup.⊖ is a compatibleanion.

The novel precursors are represented by the formula X [ (CH₂ CH₂ O--_(m)CH₂ --R--CHR'--C1]_(n), wherein X, R, R', m and n have the aforesaidmeaning. The precursors are likewise surfactants.

DETAILED DESCRIPTION OF THE INVENTION The Precursors

The precursors are prepared by reacting nonionic surfactants withbis-chloromethylated aromatics in the presence of a strong base.

Suitable nonionic surfactants leading to the precursor are describedabove and include: ethoxylated aliphatic alcohols and mercaptans, suchas the ethoxylated derivatives of decanol, dodecanol, hexadecanol,octadecanol, duodecanol, oleyl alcohol, butylbenzyl alcohol,nonylphenethyl alcohol, etc.; ethoxylated alkylphenols, such as theethoxylated derivatives of butylphenol, hexylphenol, octylphenol,dodecylphenol, octadecylphenol, and the corresponding mercaptans and thelike; polyoxyethylene esters and amides of carboxylic acids andcarboxamides, such as the esters derived by reacting ethylene oxide withdecanoic, dodecanoic, pentadecanoic, octadecanoic, cis-9-octadecenoic,cis,cis-9,12-octadecadienoic, cis,cis,cis-9,12,15-octadecatrienoic,hexylbenzoic and octylphthalic acid and the ethoxylated derivatives ofthe corresponding carboxamides, and the like; and thepolyoxyethylene-capped polymers of propylene oxide and/or butyleneoxide, such as the polyoxyethylene capped polymers of propylene oxideand/or butylene oxide initiated with methanol, ethanol, propanol,butanol or other alkanol, ethylene glycol, propylene glycol, butyleneglycol, glycerol, pentaerythritol, sorbitan, sorbitol, sucrose, etc.;and other like compounds. See pages 205-221 of the 1972 Annual of"McCutcheon's Detergents and Emulsifiers" handbook for other examplesincluded within the class of suitable nonionic surfactants for useherein. The ethoxylated derivatives of linear primary alkanols oralkenols, linear alkanoic or alkenoic acids, and alkylphenols havingfrom about 12 to about 24 carbon atoms are preferred along with thepolyoxyethylene-capped polymers of propylene oxide and/or butylene oxideinitiated with a C₁ to C₄ alkanol, ethylene glycol, propylene glycol,butylene glycol or glycerol. The ethoxylated derivatives of alkylphenolshaving from about 12 to about 24 carbon atoms are the most preferrednonionic surfactants for use herein.

The bis-chloromethylated aromatic reactants are likewise a known classof compounds. They are represented by the formula ClCH₂ --R--CHR'Cl,wherein R and R' are as defined above. Examples of suitable suchcompounds include 1-chloromethyl-3-(α-chloroethyl)benzene,1-chloromethyl-4-(α-chloroethyl)benzene and the bis-chloromethylderivatives of benzene, naphthalene, anthracene, phenanthrene, diphenyloxide, diphenyl sulfide, toluene, xylene, methylnapthalene, and thelike. There are known techniques for preparing such compounds (forexample, by reacting the aromatic compounds with chloromethyl methylether, or by reacting the bis-methylated aromatic compound withchlorine, etc.). The preferred compounds are bis-chloromethylatedderivatives of benzene, naphthalene, diphenyl oxide or diphenyl sulfide.The most preferred compounds are m- and p-bis-(chloromethyl)-benzene.

The stoichiometry of the reaction requires one mole ofbis-chloromethylated reactant per hydroxy equivalent weight of nonionicsurfactant (i.e. the mole weight of the surfactant divided by the numberof terminal hydroxyethyleneoxy groups on the surfactant molecule). Bestresults are achieved by using an excess of the bis-chloromethylatedaromatic reactant. This excess reduces the amount of undesirableby-product produced in the reaction (e.g. bis-ethers, etc.).

The reaction between the nonionic surfactants and thebis-chloromethylated aromatics is conducted in the presence of a strongbase. Suitable bases include alkali metals (e.g. sodium, potassium),alkali metal alkoxides (e.g. sodium or potassium methoxide, ethoxide,t-butoxide, etc.) and the like. The base reacts with the HCl formed inthe course of the reaction and tends to both catalyze the reaction anddrive it to completion. The amount of base used can be varied butoptimum results seem to be attained when the base is present in slightexcess of 1 equivalent of base per hydroxy equivalent weight of nonionicsurfactant.

The reaction is normally conducted with stirring at ambient conditionsof temperature and pressure for periods of from a few minutes up to afew days. Elevated temperatures will, of course, increase the reactionrate and reaction temperatures of up to about 80° C. have been used withsuccess on combinations of reactants having a low rate of reactivity.

We have found it convenient to conduct the reaction by adding thebis-chloromethylated aromatic reactant to a mixture of the nonionicsurfactant and base. A liquid reaction medium may be used, if desired,to facilitate temperature control and contact between the reactants. Anyinert solvent can be used and we have found t-butanol to be particularlyuseful in this regard.

Precursors corresponding to the general formula given above in which R'is methyl can be prepared in an analogous but alternative procedure.Namely, m- or p-vinyl-benzyl chloride can be reacted with the nonionicsurfactant to give a vinylbenzyl ether of the surfactant which in turnis reacted with HCl to give the desired product.

The Onium Surfactants

The novel onium surfactants are conveniently prepared by reacting theprecursors with an appropriate nitrogen, phosphorus or sulfur-containingorganic compound (e.g. a tertiary amine, a pyridine, a thiourea, atertiary phosphine, a sulfide, etc.). Normally this reaction isconducted in an inert liquid reaction medium (e.g. water or water/loweralkanol mixtures) and the onium product is recovered therefrom byconventional techniques. Ambient conditions of temperature and pressureare normally satisfactory but elevated temperatures (e.g. up to about80° C.) can be used advantageously in some instances. The course(extent) of the reaction can be easily followed by the production ofionic chloride.

The nitrogen and phosphorus containing organic compounds which can beused in preparing the onium surfactants have at least one reactivetertiary amino or phosphorus atom in the molecule which is quaternized.Suitable such amines therefore include those corresponding to theformulas R₁ R₂ R₃ N and R₁ R₂ R₃ P, wherein R₁, R₂ and R₃ arehydrocarbon radicals, or inertly-substituted hydrocarbon radicals,having a combined total carbon content of up to about 30 carbon atoms.Alternatively, the nitrogen atom may be a member of a heterocyclic ring.Examples of suitable such amines and tertiary phosphines include thosehaving the following R₁, R₂ and R₃ values:

                  TABLE 1                                                         ______________________________________                                        R.sub.1      R.sub.2     R.sub.3                                              ______________________________________                                        CH.sub.3     CH.sub.3    CH.sub.3                                             C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                      C.sub.4 H.sub.9                                                                            C.sub.4 H.sub.9                                                                           C.sub.4 H.sub.9                                      C.sub.10 H.sub.21                                                                          C.sub.10 H.sub.21                                                                         C.sub.10 H.sub.21                                    CH.sub.3     CH.sub.3    C.sub.12 H.sub.25                                    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           C.sub.10 H.sub.21                                    CH.sub.3     CH.sub.3    C.sub.6 H.sub.5 CH.sub.2                             C.sub.2 H.sub.5                                                                            C.sub.4 H.sub.9                                                                           C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                    CH.sub.3     C.sub.6 H.sub.5 CH.sub.2                                                                  C.sub.6 H.sub.5 CH.sub.2                             CH.sub.3     CH.sub.3    C.sub.6 H.sub.5                                      C.sub.6 H.sub.5                                                                            C.sub.6 H.sub.5                                                                           C.sub.6 H.sub.5                                      CH.sub.3     CH.sub.3    cyclohexyl                                           C.sub.4 H.sub.9                                                                            C.sub.4 H.sub.9                                                                           CH.sub.2 CH═CH.sub.2                             C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           C.sub.10 H.sub.20                                    CH.sub.3     CH.sub.3    CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           C.sub.4 H.sub.9 C.sub.6 H.sub.4 CH.sub.2             ______________________________________                                    

and other like compounds. Examples of suitable heterocyclic aminesinclude N-methylpyrrole, pyridine, quinuclidine, triethylenediamine, andthe like. The preferred amines are pyridine and trialkylamines having atotal carbon content of from 3 to about 18 carbon atoms. The preferredtertiary phosphines are triphenylphosphine and trialkylphosphines havinga total carbon content of from 3 to about 18 carbon atoms (particularlytri-n-butylphosphine).

The sulfur-containing organic compounds which can be used in preparingthe onium surfactants have at least one reactive sulfur atom in themolecule which is converted to a sulfonium species in the reaction.Suitable such compounds include those corresponding to the formula R₄SR₅, wherein R₄ and R₅ are hydrocarbon radicals or inertly-substitutedhydrocarbon radicals having a combined total carbon content of from 2 toabout 24 carbon atoms. Alternatively, R₄ and R₅ can be joined to form a5- or 6-membered heterocyclic ring. Examples of suitable such compoundsinclude those having the following R₄ and R₅ values:

                  TABLE 2                                                         ______________________________________                                        R.sub.4            R.sub.5                                                    ______________________________________                                        CH.sub.3           CH.sub.3                                                   C.sub.2 H.sub.5    C.sub.2 H.sub.5                                            C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH                                         C.sub.6 H.sub.13   C.sub.6 H.sub.13                                           CH.sub.3           C.sub.10 H.sub.21                                          CH.sub.3           C.sub.18 H.sub.37                                          CH.sub.3           C.sub.6 H.sub.5 CH.sub.2                                   C.sub.4 H.sub.9    C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                          CH.sub.3           C.sub.8 H.sub.16 --C.sub.6 H.sub.4 CH.sub.2                CH.sub.3           C.sub.6 H.sub.5                                            cyclohexyl         CH.sub.2 CH═CH.sub.2                                   CH.sub.3           C.sub.4 H.sub.8 --C.sub.6 H.sub.4 --                       ______________________________________                                    

and other like compounds. Examples of suitable heterocyclic sulfurcompounds include thiophene, tetrahydrothiophene, thiaoxane,pentamethylene sulfide, and the like. The preferred compounds aretetrahydrothiophene and dialkylsulfides having a total carbon content offrom 2 to about 18 carbon atoms and having methyl, ethyl or hydroxyethylas at least one of the two alkyl substituents.

Other suitable amino and sulfur-containing compounds include thioureaswhich correspond to the following formula: ##STR3## wherein R₆ and R₇are hydrogen or lower alkyl (C₁ to C₄). Examples of which includethiourea and the N,N'-dimethyl, N,N'-dibutyl, N,N,N',N'-tetramethylderivatives of thiourea, and the like. Of this class, thiourea is thepreferred species.

As used above, the term "inertly-substituted hydrocarbon radical" ismeant to define hydrocarbon radicals bearing one or more substituentswhich are inert in the process of preparing the onium surfactants.Examples of such inert substituents include hydroxyl, thiol, halo,cyano, and the like.

The following examples will further illustrate the invention:

EXAMPLE 1 Preparation of C₉ H₁₉ C₆ H₄ O--CH₂ CH₂ --O--₁₅ CH₂ C₆ H₄ CH₂Cl

An ethoxylated p-nonylphenol corresponding to the formula p-C₉ H₁₉ C₆ H₄O--CH₂ CH₂ O--₁₅ H (342 g., 0.4 mole) and t-butanol (3 liters) andmetallic sodium (13.8 g., 0.6 mole) were charged under a nitrogenatmosphere to a 5 liter, 3 necked flask equipped with a mechanicalstirrer, thermometer and condenser. The mixture was warmed at gentlereflux with stirring until all of the sodium had reacted.

The temperature of the mixture was then brought to 40° C. and1,4-bis(chloromethyl)benzene (350 g., 2.0 mole) was added in one shotwith stirring. The temperature exothermed less than 2° C. Aliquots ofthe mixture were taken immediately after the addition of the1,4-bis(chloromethyl)-benzene and at periods of 2 and 4 hours thereafter(aliquots 1, 2 and 3, respectively). The amount of ionic chloride(milliequivalents, meq.) in each aliquot was determined and is reportedbelow:

                  TABLE 3                                                         ______________________________________                                        Aliquot                                                                              meg. Cl.sup.⊖ /gm.                                                                         Conversion (%)*                                   ______________________________________                                        1      0.127                58                                                2      0.199                91                                                3      0.210                96                                                ______________________________________                                         *Premised on amount of sodium consumed.                                  

After a total of 4 hours at about 40° C., the mixture was filtered toremove the solids from the liquid product. The filter cake was washedwith 2 liters of benzene and the liquid wash combined with the originalfiltrate. The benzene and t-butanol solvents were removed under reducedpressure at an elevated temperature (ca. 80° C. at 5 mm. Hg.) leavingthe liquid product and unreacted 1,4-bis(chloromethyl)benzene. Thelatter compound was removed by warming the mixture at 170°-180° C. at 1mm. Hg. thereby leaving the desired product as a light yellow oil (382.4g.). Hydroxyl titration and the nuclear magnetic resonance (nmr)spectrum of this material indicated that it contained 5.7 weight percentof unreacted ethoxylated nonylphenol, 6.6 weight percent of the adductof 2 moles of ethoxylated nonylphenol and 1 mole of1,4-bis(chloromethyl)benzene and 87.7 weight percent of the desiredproduct, total weight basis in each instance. This represents a 78.8percent product yield, based on ethoxylated nonylphenol added. A 0.1weight percent aqueous solution of the product had a surface tension of32.8 dynes/cm. at 25° C. The product is therefore a surfactant.

EXAMPLES 2-11

The compounds in Table 4 were prepared following substantially theprocedure detailed in Example 1 and by using the appropriate reactants.

                                      TABLE 4                                     __________________________________________________________________________    Ex.                                                                              Product                         Yield (%)                                                                           Surface Tension                      __________________________________________________________________________    2  p-C.sub.9 H.sub.19 C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.4CH.sub.2       .sub.6 H.sub.4CH.sub.2 Cl       93    39.2                                 3  p-C.sub.9 H.sub.19 C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.9CH.sub.2       .sub.6 H.sub.4CH.sub.2 Cl       86    31.6                                 4  p-C.sub.9 H.sub.19 C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.20CH.sub.       2C.sub.6 H.sub.4CH.sub.2 Cl     65    37.8                                 5  p-C.sub.9 H.sub.19 C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.30CH.sub.       2C.sub.6 H.sub.4CH.sub.2 Cl     94    36.9                                 6  p-C.sub.9 H.sub.19 C.sub.4 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.80CH.sub.       2C.sub.6 H.sub.4CH.sub.2 Cl     100   39.8                                 7  p-C.sub.9 H.sub.19 C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.15 CH.sub       .2C.sub.6 H.sub.4OC.sub.6 H.sub.4CH.sub.2 Cl                                                                  95    34.5                                     ##STR4##                       88    36.2                                 9  n-C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.4CH.sub.2C.sub.6               H.sub.4H.sub.2 Cl               94    28.8                                 10 CH.sub.3 (CH.sub.2).sub.10 CH.sub.2 S(CH.sub.2 CH.sub.2 O).sub.15CH.sub       .2C.sub.6 H.sub.4CH.sub.2 Cl    96    33.7                                 11 CH.sub.3 (CH.sub.2).sub.10 CH.sub.2 OCH.sub.2C.sub.6 H.sub.4CH.sub.2          Cl                              94    30.3                                 __________________________________________________________________________

In some instances, the processes were conducted at 60° C. and it wasnoted that the reaction was nearly instantaneous at that temperature. Inall of the above examples, the products were viscous liquids or wax-likesolids.

EXAMPLE 12

The product of Example 3 was also prepared as follows: Metallic sodium(2.3 g., 0.10 mol) and t-butanol (400 ml.) were charged under a nitrogenblanket to a 1 liter, 3 necked flask equipped with a mechanical stirrer,thermometer, condenser and dropping funnel. After the reaction betweenthe sodium and butanol was complete, the ethoxylated nonylphenol (88.1g., 0.10 mol) was added and the temperature raised to 60° C. To this wasadded dropwise a solution of 1,4-bis(chloromethyl)benzene (17.5 g., 0.10mol) dissolved in 100 ml. benzene. The resultant slurry was maintainedat 60° C. for 2 hours. The sodium chloride produced was removed byfiltration and the solvent was stripped away under reduced pressureleaving the crude product as a straw-colored viscous liquid (96 g., 94percent yield).

EXAMPLE 13

Following the above general procedure, the compound ##STR5## wasprepared by adding a stoichiometric amount of p-vinyl-benzyl chloride(VBC) dropwise with stirring over a 1 hour period to ##STR6## int-butanol at 50° C. The reaction proceeded in about 97 percentconversion of reactants 5 hours after the addition of VBC. The t-butanolsolvent was stripped off under reduced pressure leaving the product as aviscous liquid.

The above product (50 g.) was then charged along with an equal weight ofmethanol to a reaction vessel equipped with a condensor, thermometer,mechanical stirrer, caustic scrubber and a gas sparger tube. Anhydrousgaseous HCl (55.5 g.) was then added to the solution at a constant rateover a 4 hour period. The volatiles were stripped off under reducedpressure leaving the product as a light yellow liquid weighing 49.8 g.(approximately 93 percent yield) and corresponding to the formula##STR7##

Other derivatives were similarly prepared by reacting VBC with variousnonionic (surfactants in the presence of base) and subsequent reactionwith HCl.

Other procedures for preparing the above precursors will be readilyapparent to those skilled in the art.

PREPARATION OF THE ONIUM SURFACTANTS EXAMPLE 14 Preparation of p-C₉ H₁₉C₆ H₄ O--CH₂ CH₂ O--₁₅ CH₂ --C₆ H₄ --CH₂ --S⊕--CH₃)₂ Cl⊖

A portion of the product from Example 1 (90 g., 0.088 mol) was mixedwith methanol (170 ml), water (30 ml) and dimethyl sulfide (37 ml., 0.5mol) in a sealed vessel equipped with a mechanical stirring means. Thereaction mixture was stirred at ambient temperature for several hoursand the progress of the reaction measured by titration of ionic chloridein aliquots removed from the mixture. After 46 hours the conversion ofthe reactant to the corresponding sulfonium chloride seemed to level offat about 85 percent conversion. Water (300 ml.) was added to the mixtureand any unreacted dimethyl sulfide was removed along with methanol andsome water by subjecting the mixture to a reduced pressure at ambienttemperature. The desired sulfonium chloride was thus obtained as ayellow aqueous solution containing 34 weight percent sulfonium chloridesolids. The surface tension of a 0.1 weight percent aqueous solution ofthis sulfonium surfactant was 36.3 dynes/cm. at 25° C.

Using essentially the same procedure, other onium surfactants wereprepared by reacting the precursors from Examples 1-11 withtriphenylphosphine, dimethyl sulfide, pyridine, thiourea ortriethylamine in a water/(m)ethanol medium for periods of up to about 80hours at ambient temperature. The work-up of the products wasessentially the same as above. The onium surfactants were all obtainedas aqueous solutions which, when diluted with water to a 0.1 weightpercent concentration, had surface tensions of about 43 dynes/cm. at 25°C. or less (mostly in the range of 30-40 dynes/cm.). These oniumsurfactants corresponded to the formulas in Tables 5 to 11.

                  TABLE 5                                                         ______________________________________                                         ##STR8##                                                                                                     Surface Tension                               Ex.     R               m       (dynes/cm.)                                   ______________________________________                                        14    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                15      36.3                                          15    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                4       30.7                                          16    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                7       36.9                                          17    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                9       33.9                                          18    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                20      38.8                                          19    C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                80      41.8                                          20    C.sub.11 H.sub.23 to C.sub.15 H.sub.31 mixture                                                  12      32.5                                          21    n-C.sub.12 H.sub.25 SCH.sub.2 CH.sub.2                                                          14      44.0                                          22                                                                                   ##STR9##         7       --                                            ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR10##                                                                    Ex.    Position Isomer                                                                             Surface Tension (dynes/cm.)                              ______________________________________                                        23     ortho         38.3                                                     24     meta          36.7                                                     25     para          36.3                                                     ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR11##                                                                    Ex.      m          Surface Tension (dynes/cm)                                ______________________________________                                        26       9          37.8                                                      27       15         37.6                                                      28       40         40.7                                                      ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR12##                                                                    Ex.      m          Surface Tension (dynes/cm.)                               ______________________________________                                        29       4          35.2                                                      30       7          36.6                                                      31       9          38.2                                                      32       15         39.2                                                      33       20         37.9                                                      34       40         41.7                                                      ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                         ##STR13##                                                                                                   Surface Tension                                Ex.      R            m        (Dynes/cm)                                     ______________________________________                                        35     C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                             4        35.7                                           36     C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                             7        36.6                                           37     C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                             15       35.5                                           38     C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                             20       38.6                                           39     C.sub.11 H.sub.23 to C.sub.15 H.sub.31                                                       12                                                             mixture                                                                40                                                                                    ##STR14##     7                                                       ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                         ##STR15##                                                                    Ex.             Surface Tension (dynes/cm)                                    ______________________________________                                        41              39.9                                                          ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                         ##STR16##                                                                    Ex.         R                m                                                ______________________________________                                        42        C.sub.9 H.sub.19 C.sub.6 H.sub.4                                                                 15                                               43                                                                                       ##STR17##         7                                                ______________________________________                                    

Other oniums can be similarly prepared by reacting the precursors withother tertiary amines (e.g. trimethylamine, benzyldimethylamine, etc.),with other sulfides (e.g. dipropyl sulfide, dibutyl sulfide, dodecylmethyl sulfide, benzyl methyl sulfide, diphenyl sulfide, thiophene,tetrahydrothiophene, etc.), with other thioureas (e.g.N,N,N',N'-tetramethyl (or tetraethyl) thiourea, etc.) with phosphines(e.g. tri-n-butylphosphine, trioctylphosphine, etc.), and the like.

We claim:
 1. An onium surfactant corresponding to the formula X[(CH₂ CH₂O)_(m) CH₂ -R-CHR'-Q⊕A⊖]_(n), wherein X is the hydrophobic portion of an-valent radical derived by the removal of n-atoms of active hydrogenfrom an organic compound, said organic compound being a nonionicsurfactant having a hydrophilic-lipophilic-balance of from 1 to about 30and having the structural formula X[(CH₂ CH₂ O)_(m) H]_(n) ; m is aninteger of at least 1 and is the same in each of the above formulae; Ris a divalent aromatic hydrocarbon radical of from 6 to about 14 carbonatoms, the chain length of which can be interrupted by oxygen or sulfuratoms; R' is hydrogen or methyl and is methyl only when R is m- orp-phenylene; Q⊕ is a quaternary ammonium radical corresponding to theformula --NR₂ R₃ R₃, wherein R₂, R₃ and R₄ are each independentlyhydrocarbon radicals or inertly-substituted hydrocarbon radicals andwherein the total number of carbon atoms in R₂, R₃ and R₄ does notexceed 30; A⊖ is a compatible anion; and n is an integer of from 1 to 5and is the same in each of the above formulae.
 2. The surfactant definedin claim 1 wherein n is an integer of from 1 to
 3. 3. The surfactantdefined in claim 1 wherein n is
 1. 4. The surfactant defined by claim 1wherein R is m- or p-phenylene or a divalent radical of diphenyl oxideor diphenyl sulfide.
 5. The surfactant defined by claim 1 wherein R ism- or p-phenylene.
 6. The surfactant defined by claim 1 wherein m is aninteger of from 1 to about
 200. 7. The surfactant defined in claim 6wherein m is an integer of from 4 to about
 50. 8. The surfactant definedby claim 1 wherein X is the hydrophobic portion of a n-valent radical,said radical being derived by removal of active hydrogen from anethoxylated aliphatic alcohol, phenol, organic carboxylic acid orcarboxamide, or a polyoxyethylene-capped polymer of propylene oxideand/or butylene oxide.
 9. The surfactant defined by claim 8 wherein saidradical is derived by the removal of active hydrogen from ethoxylatedalkanols, alkenols, alkylphenols, alkanoic acids or amides of alkanoicacids of from about 10 to about 24 carbon atoms orpolyoxyethylene-capped polymers of propylene oxide and/or butyleneoxide.
 10. The surfactant defined by claim 9 wherein said radical isderived by the removal of active hydrogen from an ethoxylatedalkylphenol.
 11. The surfactant defined by claim 10 wherein saidethoxylated alkylphenol is an ethoxylated nonylphenol.
 12. Thesurfactant defined by claim 11 wherein m is an integer of from 1 toabout 200, R is a divalent radical of benzene; A⊖ is halide, nitrate,sulfate, bisulfate, methylsulfate, lower alkanoate, benzoate, ortosylate, and n is
 1. 13. The surfactant defined by claim 12 wherein Q⊕is --NR₂ R₃ R₄ wherein R₂ -R₄ are alkyl and the total aggregate carboncontent of R₂, R₃ and R₄ is up to about 24 carbon atoms.